JP3444765B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to protection for semiconductor devices.
Insulating film, alignment film for liquid crystal display element, perfect for multilayer printed circuit board
The present invention relates to a photosensitive resin composition useful for forming an edge film and the like. [0002] 2. Description of the Related Art Conventionally, as a heat-resistant photosensitive material family, for example,
Materials consisting of polyamic acid and dichromate
No. 49-17374), carboxyl of polyamic acid
From those with a photosensitive group introduced into the sil group through an ester bond
Materials (JP-A-49-115541, JP-A-5-115541)
5-45746) having a polyamic acid and a photosensitive group.
Consisting of an amine compound (see JP-A-54-1457)
No. 94), the carboxyl group of polyamic acid
A material consisting of a compound having a photosensitive group introduced by a
Fees (JP-A-62-275129) and the like have been proposed.
I have. These materials use a polyimide resin precursor
After applying on a predetermined substrate,
After forming the mask, the imprint is usually performed at a temperature exceeding 300 ° C.
To obtain a heat-resistant polyimide resin film
It is. These are substrates that cannot withstand such high temperatures.
It is not suitable for forming a polyimide film on a material. On the other hand, an imidized polyimide resin
A photosensitive polyimide having a fatty acid as a basic skeleton has also been proposed.
ing. For example, as a negative type, polyimide
Example in which a functional group capable of combining is introduced (Japanese Patent Laid-Open No. 60-7292)
5, JP-A-61-59334).
Diazonaphthoquinone for polyimides
An example of blending (JP-A-3-209478) is given.
These materials do not require high temperature treatment after film formation
However, all of them are patter-toned and formed on the substrate
Adhesion between the material and the substrate is insufficient.
When applied as an electronic material, serious
Cause serious problems. [0004] SUMMARY OF THE INVENTION The present invention has the above-mentioned problems.
The purpose was to solve the problem, after pattern formation,
The imidization can be performed at a low temperature of 250 ° C. or less,
Film shows good adhesion to the substrate and
Providing highly reliable photosensitive resin compositions without the risk of metal corrosion
I do. [0005] The present inventors have achieved the above object.
As a result of intensive studies to achieve, the following composition
Easy pattern formation with good sensitivity to light irradiation
And heat treatment at a relatively low temperature of 250 ° C or less.
An imidized film can be formed on a substrate.
The film obtained by curing has heat resistance, electrical properties,
Polyimide film with excellent mechanical properties and adhesion to substrate
I found that. That is, the present invention relates to (A)
(1): [0006] Embedded image [In the formula, X is the formula (2-1), (2-2), (2-3)
And (2-4): [0007] Embedded image Wherein Y is represented by the following formula (3):
Methacryloxy group-containing divalent aromatic group 30-1
00 mol% and the divalent aromatic group 7 represented by the following formula (4)
0 to 0 mol%, [0008] Embedded image (In the formula (3), R is the formula (5): -NH-CH_TwoCH_TwoOCO-CH (CH_Three) = CH_Two (5) Selected from methacryloyl group-containing groups and hydroxyl groups represented by
And at least 50 mol% of R is of the formula
It consists of the group shown by (5). In equation (4), B is
Formulas (6-1), (6-2) and (6-3): [0010] Embedded image Selected from the groups represented by ) Z is represented by the formula (7): [0011] Embedded image (Where b is an integer of 5 to 80)
Are the divalent siloxane-containing groups shown, where m and n are integers
M / (m + n) is in the range of 0.70 to 0.98.
It is an enclosure. And a mean molecular weight of 500
100 parts by weight of 0 to 150,000 polyimide resin, and
(B) 0.01 to 20 parts by weight of a photopolymerization initiator
And a photosensitive resin composition comprising: [0013] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the composition of the present invention will be described in detail.
I will tell.(A) Polyimide resin (A) a polyimide resin used as a component
In the general formula (1), the tetravalent group represented by X is represented by the formula (2-
Any of 1) to (2-4) may be used, and two or more kinds may be mixed.
May be. In a divalent group represented by Y,
The methacryloyl group-containing group of (3) is essential, and
30-100 mol%, preferably 50-100 mol%
Occupy. When the group of the formula (3) is less than 100 mol%,
Is a group of the formula (4). 30 mol% of the group of the formula (3)
If it is less than 1, the exposed portion does not show sufficient photocurability, and
I can't get a turn. In the group of the formula (3), R represents the above-mentioned formula (5)
A methacryloyl group-containing group or a hydroxyl group, provided that the formula
The group of (5) is at least 50 mol%, preferably 80 to 10
0 mol%. The groups represented by B are represented by the formulas (6-1) to (6-
3) selected from the groups represented by
They may be mixed. Preferably, it is a group of the formula (6-2)
You. The group represented by Z is a siloxane-containing group of the formula (7)
In the formula (7), b is from 5 to 80, preferably from 8 to
It is an integer of 75. If b is less than 5, the elastic modulus of the resin film
High protective film for electronic components such as semiconductor devices
Is difficult to apply, and if it exceeds 80, the siloxane component
It becomes insoluble in the system and the polymerization reaction does not proceed. In the general formula (1), a structural unit containing Y
And the number of structural units containing Z (n) are both
M is 70 to 98 mol% and n is 2 to 3 in the total of the units.
0 mol%. Preferably, m is 80 to 98 mol%,
n is 20 to 2 mol%. When m is less than 70 mol%,
The strength of the resin film decreases, making it unsuitable as a protective film.
Yes, if over 98 mol%, poor adhesion to substrate
You. In addition, m is usually 1 to 500 (preferably 3 to 30).
0) and n is 1 to 200 (preferably 1 to 1)
00). This polyimide resin, for example,
It can be manufactured as follows. General formula (8): [0017] Embedded image [Wherein, X is as described above] And an acid anhydride represented by the general formula (9): H_TwoN-Y'-NH_Two            (9) [In the formula, Y ′ is the formula (10): [0019] Embedded image Divalent having a carboxyl group represented by
Selected from an aromatic group and a divalent aromatic group represented by the formula (4).
Devour. An aromatic diamine compound represented by the general formula
(11): H_TwoNZ-NH_Two        (11) [Wherein, Z is as defined above]
Polyimide is synthesized by a standard method using
You. This synthesis may be performed according to a conventional theory, but the reaction solvent
Is used in the solution composition of the polyimide resin of the present invention described later.
Organic solvents similar to those used, especially N-methyl-2
Loridone, cyclohexanone and the like can be suitably used. Anti
The reaction is carried out at room temperature (e.g.
After dissolving the substance and the diamine, they are reacted to form a polyamic acid.
After that, add a dehydrating solvent such as toluene or xylene to the reaction solution.
And heated to about 130 to 200 ° C. to carry out dehydration condensation.
And perform polyimide. Cool this to polyimide resin
Get. The polyimide resin thus obtained has the formula (1)
2): [0022] Embedded image Wherein X, Y ′, Z, m and n are as described above.
Has a structure that is Next, the carboxyl group of Y 'in the formula (12)
By introducing a methacryloyl group into the general formula
Obtain the resin of (1). How to guide this methacryloyl group
Although there is no limitation, for example, isocyanatoethyl methacrylate
And methylenebis (4-amino-3-benzoic)
Acid) by reaction with carboxyl groups
You. This reaction proceeds at room temperature without a catalyst. Generated resin
50 mol% or more of R is a methacryloyl-containing group of the formula (5)
So that In the above synthesis, the acid anhydride of the general formula (8)
As the hydrate, 1 selected from four kinds of compounds having different Xs
The desired polyimide structure can be obtained from one or more kinds
Can be used. Diamine compound of general formula (9)
The compound is a group of the general formula (3) in the divalent group Y and the general formula
It is used so that the ratio with the group of (4) becomes a desired value.
The siloxane group-containing diamine compound of the general formula (11)
In order to obtain the desired m / (m + n) value,
The use ratio with the component is adjusted. Diamine compound forming a group of the general formula (3)
As a product, for example, methylenebis (4-amino-3-
Benzoic acid), methylene bis (4-amino-
2-benzoic acid), methylene bis (3-amido)
No-4-benzoic acid). A diamine compound forming a group of the formula (4)
For example, for example, 1,4-bis (3-aminophenoxy)
B) benzene, l, 4-bis (4-aminophenoxy)
Benzene, 2,2-bis [4- (4-aminophenoxy)
Cis) phenyl] propane, 2,2-bis [4- (4-A
Minophenoxy) phenyl] perfluoropropane
However, the present invention is not limited to these. Preferred
Or 2,2-bis [4- (4-aminophenoxy) phenyl
Enyl] is propane. [0027](B) Photopolymerization initiator The following are specific examples of the photopolymerization initiator.
However, the present invention is not limited to these. Benzo
Phenone, acetophenone, anthrone, phenanthrene
, Nitrofluorene, ditroacenaphthene, p, p '
-Tetramethyldiaminobenzophenone, p, p'-
Tetraethyldiaminobenzophenone, chlorothioxa
N-ton, benzanthraquinone, 2,6-bis- (4-
Diethylaminobenzal) -cyclohexanone, 2,6
-Bis- (4-diethylaminobenzal) -4-methyl
-Cyclohexanone, 4,4'-bis- (diethylamido
G) chalcone, 2,4-diethylthioxanthone, N-
Phenyl-diethanolamine, diethylaminoethyl
Methacrylate, coumarin compound benzyl, benzoin
Isopropyl ether, 1-hydroxy-cyclohexyl
Le-phenyl ketone, 2-methyl- [4- (methylthio
E) phenylco-2-morpholino-1-propane, 1
-Phenyl 1,2-butanedione-2- (o-methoxy
Carbonyl) oxime, N-phenylglycine, 3-f
Enyl 5-isoxazolone, camphorquinone, bimida
Sols These may be used alone or in combination of two or more.
can do. The component (B) is a resin 1 of the component (A).
0.0l parts by weight to 20 parts by weight based on 00 parts by weight
And preferably 0.05 to 5 parts by weight. [0028]Other ingredients The components of the composition of the present invention are usually dissolved in an organic solvent,
Apply to substrate in the state (as polyimide resin solution composition)
Is done. As the solvent used, a polyimide precursor
The solvent used for the synthesis is preferably used. So
Specific examples of N-methyl-2-pyrrolidone,
Tylacetamide, dimethylformamide, hexamethyl
Ruphosphoramide, tetrahydrofuran, 1,4-di
Xan, methyl cellosolve, butyl cellosolve, diechi
Len glycol dimethyl ether, diethylene glycol
Diethyl ether, triethylene glycol dimethyl
Ether, acetone, methyl ethyl ketone, methyl iso
Butyl ketone, cyclopentanone, cyclohexanone,
2-heptanone, 2-octanone, 7-butyrolact
Butyl cellosolve acetate, toluene, xylene
, Anisole, methylanisole, ethylphenyle
Or one or more of these.
The above can be used in combination. Also, the amount of solvent used
Is relative to the total amount of the polyimide resin (A) and the solvent.
And the polyimide resin of the component (A) is 5 to 50% by weight.
Is preferred. [0029]Usage / Use The composition of the present invention is usually spin-coated in the above-mentioned solution state.
Substrate (or substrate) by known methods such as
It is applied to Substrates include silicon wafers, metals
There are a plate, a glass sheet, a ceramic substrate and the like. After application, dry
Use heating means such as a dryer or hot plate,
Prebake at a temperature of ~ 180 ° C for several minutes to several hours,
By removing most of the solvent in the coating film,
A product film can be obtained. Put a mask on this coating
Place, irradiate light such as visible light, ultraviolet light for several seconds to several minutes,
Next, by dissolving and removing the unexposed portion with a developer,
A relief pattern can be obtained. Also at this time
As the developer used for the above, a solvent for the above composition is used.
Solvent used alone or in combination of two or more
Can be used. Furthermore, formed by development
The resin of the relief pattern
Because it is in the form of fat, it can be dried or used in an electric furnace
150 to 250 ° C, especially 150 to 20
By heating at a temperature of 0 ° C. for several tens of minutes to several hours,
Just put off the solvent, sensitizer and polymerization initiator
Can be formed. The photosensitive resin composition of the present invention can be easily patterned.
Can be formed, and the resin skin formed after heating
Because the film has excellent heat resistance, mechanical properties, and electrical properties
In addition, it can be suitably used as a protective film for electronic components.
You. As the protective film for electronic parts, for example, a semiconductor device
Device, specifically, diode, transistor, IC, L
Junction coating film on the surface of semiconductor devices such as SI,
Passivation film, buffer coat film, LSI etc.
α-ray shielding film, interlayer insulation film for multilayer wiring,
Circuit board conformal coat, liquid product display
There are a wide range of devices including alignment films for devices and ion implantation masks.
Can be used over a range. [0031] EXAMPLES The present invention will be described below in more detail with reference to Examples.
As will be explained, the present invention is limited to the following examples.
There is no. [Synthesis Example 1] Stirrer, thermometer, nitrogen purging device and esthetic
2,2-bis in a flask equipped with an adapter
(3,4-benzenedicarboxylic anhydride) perf
Luoropropane 44.42 g (0.100 mol), solvent
Was charged with 250 g of cyclohexanone. This solution
While stirring, then from the dropping funnel in the formula (11)
27.00 g of a siloxane-containing diamine where b is 9.8
(0.030 mol) was added dropwise.
Methylene bis (4-amino) dissolved in 100 g of xanone
20.02 g (0.07 g of -3-benzoic acid)
0 mol) was added dropwise. Stir for another 10 hours after dropping
Continued. Thereafter, 50 g of toluene was added to the reaction solution,
The system was heated to 150C. At this time ester adapter
Through which 3.5 g of water was recovered. After heating, room temperature
And the target structure represented by the following formula (13)
To obtain a resin solution. When the IR spectrum of this resin was observed,
1780cm^-1And 1720cm^-1Based on imide group
Absorption is 3300cm^-lPhenol group nearby
Was observed. Dissolve tetrahydrofuran
The gel permeation chromatograph
When the molecular weight was measured, the weight average was calculated in terms of polystyrene.
The molecular weight was 45,000. [0033] Embedded image X: [0034] Embedded image Y: [0035] Embedded image Z: [0036] Embedded image 280 g of the resin solution thus obtained
Into a flask, and add isocyanatoethyl meta
8.65 g of acrylate was added dropwise at room temperature. During dripping, solution
And the generation of carbon dioxide gas was observed. Dripping
After completion, the mixture was further stirred at room temperature for 4 hours,
Introduction of methacryloyl group (to 50 mol% of -COOH
Introduction), the desired resin corresponding to the component (A) of the present invention
(Referred to as a-1) was obtained. (Resin solid content about 24 layers
amount%) [Synthesis Example 2] Tetracarbo
3,3 ', 4,4'-biphenyl as dianhydride
8.83 g (0.030 mol) of tetracarboxylic anhydride
And 1,3-bis (3,4-dicarboxyphenyl)-
1,1,3,3-tetramethyldisiloxane dianhydride
29.82 g (0.070 mol) of L, N as a solvent
-Methyl-2-pyrrolidone 250 g, aromatic diamine and
To methylene bis (4-amino-3-benzoic acid)
Sid) 14.3 g (0.050 mol), 1,3-bis
13.15 g of (3-aminophenoxy) benzene (0.
045 mol), and b in formula (11) is 75
28.62 g of siloxane-containing diamine (0.005
) And N-methyl-2-pyrrolidone 110 as a solvent.
g (total 360 g), except that g was used.
Thus, a resin solution having an average molecular weight of 82,000 was obtained. This
14. Isocyanatoethyl methacrylate is added to the resin solution of 15.
A methacryloyl group was introduced using 5 g (-COOH
100 mol% based on the total). Thus, (A) of the present invention
A solution of a resin corresponding to the component (referred to as a-2) was obtained. [Synthesis Example 3] Tetracarbo
4,4'-oxyphthalic anhydride as the acid dianhydride
15.51 g (0.050 mol) of hydride and 1,3
-Bis (3,4-dicarboxyphenyl) -l, 1,
3,3-tetramethyldisiloxane dianhydride 2
1.30 g (0.050 mol), cyclohexane as a solvent
255 g of xanone, methylenebi as aromatic diamine
(4-amino-3benzoic acid) 11.44
g (0.040 mol), 2,2-bis [4- (4-amido)
Nophenoxy) phenyl] propane 16.42 g (0.
04 mol), and b is 9.8 in the formula (11).
16.20 g of siloxane-containing diamine (0.018
), And siloxa wherein b in formula (11) is 75
Diamine 11.45 g (0.002 mol) as solvent
Except that 100 g of N-methyl-2-pyrrolidone was used.
Is a tree having an average molecular weight of 23,000 in the same manner as in Synthesis Example 1.
A solution of the fat was obtained. Isocyanatoethyl methacrylate
A methacryloyl group was introduced using 12.4 g of
(Introduced 100 mol% based on -COOH). Thus obtained
A solution of the resin corresponding to the component (A) of the present invention (a-
3). [Synthesis Example 4] An acid anhydride was used as a raw material.
3,3 ', 4,4'-benzophenonetetracarboxylic
32.23 g (0.100 mol) of acid dianhydride as a solvent
250 g of N-methyl-2-pyrrolidone,
As the amine, methylene bis (4-amino-3-benzo
Ic Acid) 14.3 g (0.050 mol),
8.91 g of 4,4'-methylenedianiline (0.04
5 mol) and siloki wherein b is 75 in formula (11)
28.62 g (0.005 mol) of a sun-containing diamine,
As a solvent, N-methyl-2-pyrrolidone 110 g
(Synthesis Example 1) except that (total 360 g) was used.
To obtain a polyimide resin solution with an average molecular weight of 60,000
Was. Isocyanatoethyl methacrylate is added to this resin solution.
  A methacryloyl group was introduced using 15.5 g (-
100 mol% based on COOH). Thus obtained
The resin solution is referred to as (a-4). [Synthesis Example 5] An acid anhydride was used as a raw material.
2,2-bis (3,4-benzenedicarboxylic acid anhydride)
(Doride) perfluoropropane 44.42 g (0.1
00 mol) and cyclohexanone 250 as a solvent.
g, a siloxanedia of the formula (11) wherein b is 98
27.00 g (0.030 mol) of min, methylene bis
(4-amino-3-benzoic acid) 20.0
2 g (0.070 mol), and cyclohexanone 10
Average molecular weight in the same manner as in Example 1 except that 0 g was used.
45,000 polyimide resin solutions were obtained. This resin melt
6.51 g of isocyanatoethyl methacrylate is added to the liquid.
To introduce a methacryloyl group (versus -COOH).
30 mol%). The resin solution obtained in this manner was (a-
5). [Synthesis Example 6] As an acid anhydride, 2,2-bi
(3,4-benzenedicarboxylic anhydride) par
44.42 g (0.100 mol) of fluoropropane, dissolved
As an agent, cyclohexanone 250 g, methylenebis
(4-amino-3-benzoic acid) 17.1
6 g (0.060 mol), and in the formula (11), b is 75
228.96 g of siloxane diamine (0.04
0 mol) and 100 g of cyclohexanone.
Was performed. However, a heterogeneous yellow-white cloudy solution was obtained.
Only to obtain a uniformly polymerized polyimide resin solution.
Did not. Examples 1 to 6 and Comparative Examples 1 and 2
As in each case, one of the trees
To 100 parts of the fat solution, the photopolymerization initiator was added in the amount shown in the table.
To prepare the composition. Spin coater the resulting composition
Apply to silicon wafer using
At 90 ° C. for 4 minutes. Stripe coating on the resulting coating
A photo mask with a turn is adhered, and the
Ultraviolet light from a high pressure mercury lamp was irradiated for 60 seconds. Next, N
-Methyl-2-pyrrolidone / xylene = 50/50 solution
The solution was developed for 30 seconds and rinsed with xylene. The obtained line and space pattern
By observing the shape of the
To evaluate the photosensitivity. Also, dry the obtained pattern
Curing at 150 ℃ / 0.5hour and 200 ℃ / 1hour in oven
And then 24:00 during a 2 atm pressure cooker
Cross-cut peeling test for adhesion to wafer after standing for a while
(JIS5400). The results are shown in Table 1. [0046] [Table 1](note) α: ethyl 4-diethylaminobenzoate β: diethylaminoethyl methacrylate γ: 2,6-bis (4-diethylaminobenzal) -4
-Methylcyclohexanone δ: carbonyl bis (diethylaminocoumarin) ε: N-phenylglycine ζ: 3-phenyl 5-isoxazolone η: 2,2-bis (o-chlorophenyl) -4,5
4 ', 5'-tetraphenyl-1,2'-biimidazo
Le As is clear from the results in Table 1, Example 1
The solutions of the resin compositions (1) to (4) are applied to relatively thick films.
It has good photosensitivity and good pattern after development.
Silicon wafer by heat treatment at low temperature
A film having excellent adhesiveness to the film was formed. [0048] As described above, the photosensitive tree of the present invention
The fat composition has excellent storage stability and good feeling
And easily heat-treated by low-temperature heat treatment.
Gives a turned resin film. Furthermore, this putter
Heat-resistant, electrical and mechanical properties, substrate
Made of polyimide resin with excellent adhesion to
It can be suitably used as a protective film for components.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-100143 (JP, A) JP-A-1-283554 (JP, A) JP-A-5-247211 (JP, A) JP-A 8- 272098 (JP, A) JP-A-9-100350 (JP, A) JP-A-10-265571 (JP, A) JP-A-10-274850 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 G03F ^7/ 00-7/42 C08L 79/00-79/08 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] (A) General formula (1): [In the formula, X is the formula (2-1), (2-2), (2-3)
And (2-4): Y is a divalent aromatic group containing a methacryloxy group represented by the following formula (3):
00 mol% and the divalent aromatic group 7 represented by the following formula (4)
0 to 0 mol%, (In the formula (3), R is formula _{(5): -NH-CH 2} CH 2 OCO-CH (CH 3) = CH 2 (5) a group selected from a methacryloyl group-containing group and a hydroxyl group represented by (5), and at least 50 mol% of R is a group represented by the formula (5). In the formula (4), B is represented by the formulas (6-1), (6-2) and (6-3): Selected from the groups represented by Z is represented by the formula (7): (Where b is an integer of 5 to 80), and m and n are integers,
m / (m + n) is in the range of 0.70 to 0.98. ]
Having a structure represented by the following formula, having an average molecular weight of 5,000 to 150,
A photosensitive resin composition comprising 100 parts by weight of a 2,000 polyimide resin and 0.01 part by weight to 20 parts by weight of a photopolymerization initiator (B).